Fire resistant compound



Unite 3,070,604 HERE RESESTANT CGMPOUND Folsom E. Drnmmond, Washington, DAL, assignor to Basic Research Corporation, Dayton, Ohio, at corporation of Delaware No Drawing. Filed July 26, 1960, Ser. No. 45,302

9 Claims. (Cl. 260313) This invention relates to a new and useful Class of compounds and their preparation, and more particularly to pyrrylamidophosphates and polymers thereof. Such compounds and their polymers are useful as chemical intermediates, and as adhesives, lubricants, pharmaceuticals, cosmetics and Water-treating materials, and fire and ham: resistant substances.

The invention comprises five-membered heterocyclic compounds having the general structural formula:

where PN represents the amidophosphate structure where x is hydrogen, alkyl or aryl radical, y is hydrogen,

alkyl or aryl radical, and where 1: may be the same or W Jr,

different from y.

The corresponding polymer structure is represented by the formula:

0, FT] II em} i where x and y having the values given and n is an integer from 1 to 8 and higher.

Patented Dec. 25, 19-32 The pyrramidophosphates of this invention may be prepared by reacting a pyrrole with an amidophosphoryl chloride and separating the resultant pyrrylamidophosphate from the reaction mixture. The compounds of the invention are suitably prepared starting with hydroxy pyrrylmagnesium bromide and reacting the same with amidophosphorylchloride to form the corresponding pyrrylamiclophosphate and magnesium bromyl chloride.

The equation for this reaction is illustrated as follows:

The polyesters of pyrrylamidophosphate may be obtained by condensation of hydroxyl pyrrole with amidophosphoric acid, the condensation reaction being carried out by heating the mixture at temperatures between 200 and. 350 C. for three to six hours. The following equation illustrates the reaction to form a polyester structure as in the case of the amine pyrrylphosphate.

The invention is further exemplified by the following examples which it Will be understood are not limitative of the invention. The parts are by weight unless otherwise indicated.

EXAMPLE 1 Z-Pyrrylamidophosphate A mixture comprising one molecular equivalent part (1 mole) in grams of hydi'oxy pyrrylmagnesium bromide and one molecular equivalent part (1 mole) in grams of amidophosphoryi nionochloride is reacted at a temperature of 200 C. for one hour in the presence of 0.1 gram of magnesium chloride, the reaction being carried out under an inert atmosphere of nitrogen. The reaction -r A e,- 4. product recovered by filtering and fractional distillation The polymers may be used in different physical forms of the residue consists of pyrrylamidophosphate in fabricating various products. They may be drawn into WM 3 fibers and filaments and fashioned in fabrics and the like it Si {,l' to provide fireproof materials. i l 5 In place of employing catalysts such as magnesium is l i chloride, the equivalent alkali metal halide compounds W p may be used such as calcium, beryllium, Zinc, or alu- N l minum or titanium.

H The compounds of the present invention may be modi- NH2 tied by various substitute products, particularly with re- EXAMPLE 2 spect to the amidophosphate reactant to form derivatives or the amtdopyrrylpnosphates.

W p p lymer The foregoing invention has been described with particular reference to the amidopyrrylphosphate compounds,

1,; but it will be understood that derivative amido compounds of the pyrrylphosphate structure as hereinbefore illustrated and described is within the spirit and scope of this invention, and as described hereinabove and defined in the appended claims.

What is claimed is:

The reaction product of Example 1 is polymerized by heating the reactant mixture at a temperature of 200 C. for three hours to obtain a polymer having the basic molecular structure ii C l. A compound of the formula H Q l O i \l I I M l l O k. l l H na l K t n N a a EXAMPLE 3 H 2 In this example the reaction is carried out similarly 39 as described in Example 1, except that dimethyl amidophosphate is used in place of amidophcsphate to produce 2. A compound of the formula the corresponding dimethyl amidopyrrylamidophosphate. The structure is illustrated as follows: ll l- Where x is selected from the group consisting of hy- CH drogen, lower alkyl and benzyl radical and y is selected from the group consisting of hydrogen, lower alkyl and EXAMPLE 4 .5 y In this example the reaction is carried out similarly A compound of the formula as in Example 1, using diethylarnidophosphate in place rof amidophosphate to form the corresponding diethylj pyrrylamidophosphate. The structure is illustrated as i i] follows: M l i l t a, i i i i il a l t e er it i i \a/ I u M -Qt; t H t N m N 2 i H (IEHS where n is at least 2.

C2H A method of preparing a pyrrylamidophosphate EXAMPLE 5 G0 which comprises reacting a hydroxy pyrrylmagnesiurn bromide with an amidophosphoryl chloride at a temperature of 200 C. under an inert atmosphere, and recovering the resultant pyrrylamidophosphate reaction product.

5. A method of preparing a pyrrylamidophosphate polymer which comprises reacting a hydroxy pyrrylmagnesium bromide with an amidophosphoryl chloride at a In this example the reaction is carried out as described in Example 1, using dibenzyl amidophosphate as the reactant with the hydroxy pyrrole to form the corresponding aryl derivative. The structure is illustrated as fola temperature of 200 C. for 3 to 4 hours under an inert atmosphere, and recovering the resultant pyrrylarnidophosphate polymer reaction product.

1 O p QH 6. A method of preparing polyesters of pyrrylamidophosphate comprising heating a hydroxy pyrrole with an H 65% amidophosphoric acid for several hours at a reaction N temperature of 200 to 300 C. under an atmosphere of nitrogen, and separating the resultant polyester formed.

Cgl'i; 7. A method of preparipg pyrrylarnidophosphates as 3,070,604 5 in claim 6, wherein the phosphate reactant is dimethyl in claim 6, wherein the phosphate reactant is dibenzyl amidophosphate. amidophosphate.

8. A method of preparing pyrrylamidophosphates as in claim 6, wherein the phosphate reactant is diethyl References Cited m the file of thls patent 'amidophosphate. 5 UNITED STATES PATENTS A method of preparing pyrrylamidophosphates as 2 14 5 4 Lipkin 7,1937

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1. A COMPOUND OF THE FORMULA 